Herbicidal N-(heterocyclicaminocarbonyl)-ortho-haloalkylbenzenesulfonamides

ABSTRACT

N-(heterocyclicaminocarbonyl)-ortho-haloalkylbenzenesulfonamides, such as 2-(dichloromethyl)-N-[(4-methoxy-6-methylprimidin-2-yl) aminocarbonyl]-benzenesulfonamide, are useful as preemergent or postemergent herbicides or as plant growth regulants.

RELATED APPLICATION

This application is a continuation-in-part of my copending applicationSer. No. 259,982, filed May 12, 1981, now abandoned, which is acontinuation-in-part of Ser. No. 168,892, filed July 11, 1980, nowabandoned.

BACKGROUND OF THE INVENTION

This invention relates to o-haloalkylbenzene sulfonyl ureas which areuseful as herbicides.

Netherlands Pat. No. 121,788, published Sept. 15, 1966, teaches thepreparation of compounds of Formula (i), and their use as general orselective herbicides, ##STR1## wherein R₁ and R₂ may independently bealkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbonatoms.

Compounds of Formula (ii), and their use as antidiabetic agents, arereported in J. Drug Res. 6, 123 (1974). ##STR2## wherein R is pyridyl.

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products that satisfy man's basic foodneeds, such as soybeans, corn, wheat, and the like. The currentpopulation explosion and concomitant world food shortage demandimprovements in the efficiency of producing these crops. Preventing orminimizing the loss of a portion of such valuable crops by killing orinhibiting the growth of undesired vegetation is one way of improvingthis efficiency.

A wide variety of materials useful for killing or inhibiting(controlling) the growth of undesired vegetation is available; suchmaterials are commonly referred to as herbicides. The need still exists,however, for more effective herbicides that destroy or retard weedswithout causing significant damage to useful crops.

In U.S. Pat. No. 4,127,405 compounds of the following formula aretaught: ##STR3## wherein R₁ is ##STR4## R₃ and R₆ are independentlyhydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1-4 carbonatoms, alkoxy of 1-4 carbon atoms, nitro, trifluoromethyl, cyano, CH₃S(O)_(n) -- or CH₃ CH₂ S(O)_(n) --;

R₄ is hydrogen, fluorine, chlorine, bromine or methyl;

R₅ is hydrogen, fluorine, chlorine, bromine methyl or methoxy;

R₇ is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atomsor alkoxy of 1-2 carbon atoms;

R₈ is hydrogen, methyl, chlorine or bromine;

R₉ and R₁₀ are independently hydrogen, methyl, chlorine or bromine;

W and Q are independently oxygen or sulfur;

n is 0, 1 or 2;

X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbonatoms, trifluoromethyl, CH₃ S-- or CH₃ OCH₂ --; and

Z is methyl or methoxy;

or their agriculturally suitable salts;

provided that:

(a) when R₅ is other than hydrogen, at least one of R₃, R₄, R₆ and R₇ isother than hydrogen and at least two of R₃, R₄, R₆ and R₇ must behydrogen;

(b) when R₅ is hydrogen and all of R₃, R₄, R₆ and R₇ are other thanhydrogen, then all of R₃, R₄, R₆ and R₇ must be either chlorine ormethyl; and

(c) when R₃ and R₇ are both hydrogen, at least one of R₄, R₅ or R₆ mustbe hydrogen.

SUMMARY OF THE INVENTION

This invention relates to novel compounds of Formula I and theiragriculturally suitable salts, e.g. Na, K, ammonium, alkyl ammonium,suitable agricultural compositions containing them, and their method ofuse as pre-emergence and post-emergence herbicides. ##STR5## wherein Lis Cl, F, Br, NR₃ R₄, N⁺ R₃ R₄ R₄ ', N(R₄)C(O)R₅, N(R₄)C(O)NHR₆ orN(R₄)C(O)OR₇ ;

R is H, F, Cl, Br, NO₂, CF₃, C₁ -C₃ alkyl or C₁ -C₃ alkoxy;

R₁ is H,F,Cl or C₁ -C₄ alkyl;

R₂ is H or CH₃ ;

R₃ is H, C₁ -C₄ alkyl or OCH₃ ;

R₄ is H or C₁ -C₄ alkyl;

R₃ and R₄ can be taken together to form --(CH₂)₄ --, --(CH₂)₅ -- or--(CH₂)₂ O(CH₂)₂ --;

R₄ ' is H, CH₃ or CH₂ CH₃ ;

R₅ is C₁ -C₄ alkyl optionally substituted with 1-3 atoms of F, Cl or Br,or C₃ -C₄ alkenyl;

R₆ is H, C₁ -C₄ alkyl or C₃ -C₄ alkenyl;

R₇ is C₁ -C₄ alkyl;

R₈ is H, CH₃ or OCH₃ ;

A is ##STR6## W is O or S; X is H, Cl, Br, CH₃, CH₂ CH₃, C₁ -C₃ alkoxy,CF₃, SCH₃ or CH₂ OCH₃ ;

Y is CH₃ or OCH₃ ;

Z is N, CH, CCl, CBr, CCN, CCH₃, CCH₂ CH₃, CCH₂ CH₂ Cl or CCH₂ CH═CH₂ ;

Y¹ is H, CH₃, OCH₃ or OCH₂ CH₃ ; and

Q is O or CH₂ ;

and their agriculturally suitable salts;

provided that:

(1) when R₁ is Cl, then L is Cl or Br and R₂ is H;

(2) when R₃ is OCH₃, then R₄ is CH₃ ;

(3) when W is S, then R₈ is H; and

(4) when L is F, then R₁ is H, F, or C₁ -C₄ alkyl.

Preferred Compounds

Preferred in increasing order for their higher activity and/or morefavorable ease of synthesis are:

(1) compounds of generic scope wherein Z is N, CH, CCl, CBr or CCH₃, Wis O, and R₈ is H or CH₃ ;

(2) compounds of preferred (1) wherein Z is CH or N and X is CH₃ of OCH₃;

(3) compounds of preferred (2) wherein A is ##STR7## L is Cl, Br or NR₃R₄ and R₈ is H; (4) compounds of preferred (3) wherein R₁ and R₂ are H;

(5) compounds of preferred (4) wherein R is H; and

(6) compounds of preferred (5) wherein L is Cl or Br.

Specifically preferred for highest activity and/or most favorable easeof synthesis are:

2-(Dichloromethyl)-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide;

2-(Dichloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide;

2-(Dichloromethyl)-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide;

2-(Chloromethyl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide;

2-(Chloromethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide;

2-(Chloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide;

2-(1-Chloroethyl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide;

2-(1-Pyrrolidinylmethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide,hydrochloride; and

2-(1-Pyrrolidinylmethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide.

This invention also relates to novel compounds of Formula II which areuseful intermediates for the preparation of the herbicidal compounds ofFormula I. ##STR8## wherein R, R₁, R₂ and L are as previously defined;and

Z is CH or N;

provided that

(1) when R₁ is Cl, then L is Cl or Br and R₂ is H;

(2) when L is NR₃ R₄ or N⁺ R₃ R₄ R₄ ', then R₃ or R₄ can not be H; and

(3) when R₃ is OCH₃, then R₄ is CH₃.

This invention also relates to novel compounds of Formula IV which areuseful intermediates for the preparation of the compounds of Formula I.##STR9## wherein R, R₁ and R₂ are as previously defined; and L is Cl, F,Br, NR₃ R₄ or N⁺ R₃ R₄ R₄ '.

provided that

(1) when R₁ is Cl, then L is Cl or Br and R₂ is H;

(2) when L is NR₃ R₄ or N⁺ R₃ R₄ R₄ ', then R₃ and R₄ cannot be H; and

(3) when R₃ is OCH₃, then R₄ is CH₃.

Synthesis

As shown in Equation 1, the compounds of Formula I where W=0, can beprepared by combining an appropriate 2-aminoheterocycle of Formula Vwith an appropriately substituted sulfonyl isocyanate of Formula IV R,R₁, R₂, R₈, L and A being as previously defined and L is Cl, Br, NR₃ R₄and NR₃ R₄ R₄ ' where R₃, R₄ and R₄ ' are as previously defined providedR₃ and R₄ cannot be H. ##STR10##

The reaction is best carried out in inert aprotic organic solvents suchas methylene chloride, tetrahydrofuran or acetonitrile, at ambientpressure and temperature. The mode of addition is not critical; however,it is often convenient to add the sulfonyl isocyanate to a stirredsuspension of the aminoheterocycle. Since isocyanates usually areliquids, their addition is more easily controlled.

The reaction is generally exothermic. In some cases, the desired productis insoluble in the warm reaction medium and crystallizes from it inpure form. Products soluble in the reaction medium are isolated byevaporation of the solvent, trituration of the solid residue withsolvents such as 1-chlorobutane, ethyl ether, or pentane, andfiltration.

The intermediate sulfonyl isocyanates of Formula IV can be prepared byreacting corresponding sulfonamides with phosgene in the presence of analkyl isocyanate such as butyl or cyclohexyl isocyanate at reflux in asolvent such as chlorobenzene, according to the procedure of H. Ulrichand A. A. Y. Sayigh, Newer Methods of Preparative Organic Chemistry,Vol. VI, p. 223-241, Academic Press, New York and London, W. Foerst, Ed.In cases where formation of the desired sulfonyl isocyanate is difficultby the above procedure, the preformed sulfonylurea from the reaction ofbutyl isocyanate with the appropriate sulfonamide is contacted withphosgene according to the above reference.

Alternatively, the process of Ulrich and Sayigh can be improved by theaddition of a tertiary base to the reaction mixture as shown by Equation2. R, R₁, R₂ and L are as previously defined above in Equation 1.##STR11##

A mixture of the appropriate benzenesulfonamide III, an alkyl isocyanatesuch as butyl isocyanate and a catalytic amount of 1,4-diaza[2,2,2]bicyclooctane (DABCO) in xylene or other inert solvent ofsufficiently high boiling point (e.g. >135°) is heated to approximately135°. Phosgene is added to the mixture until an excess is present asindicated by a drop in the boiling point. (The mixture is heated furtherto drive off the excess phosgene.) After the mixture is cooled andfiltered to remove a small amount of insoluble by-products, the solventand alkyl isocyanate are distilled off in vacuo leaving a residue whichis the crude sulfonyl isocyanate IV.

The preparation of sulfonamides from ammonium hydroxide and sulfonylchlorides is widely reported in the literature, e.g. Crossley et al., J.Am. Chem. Soc., 60, 2223 (1938).

For those examples containing reactive functionality in the positionortho to the sulfonamide moiety, it is convenient to add the sulfonylchloride to a measured quantity of ammonia (Equation 3) in an inertsolvent, e.g. tetrahydrofuran, ethyl acetate, etc., at low temperature(-78° to 0°). Side reactions such as ring formation, elimination, orcondensation are thereby substantially avoided. ##STR12## L'=Cl, Br R,R₁ and R₂ as above.

The α-haloalkylbenzenesulfonamides may be converted to other requiredintermediates for this invention by treatment with appropriate reagentsas described in Equation 4 and Example 18. ##STR13## R₁ '=H, C₁ -C₄alkyl L'=Cl, Br

The various intermediates i serve as precursors to other requiredcompounds of this invention.

Ammonium salts can be prepared by alkylation as described in Equation 5and Example 19. ##STR14##

Various amides, ureas and carbamates may be produced by well-knownreactions of the primary or secondary amine i (at least one of R₃ and R₄is H) with the desired acyl chloride, carbamoyl chloride, orchloroformate (Equation 6): ##STR15##

Certain sulfonyl chlorides are best prepared by chlorosulfonation of asubstituted benzene according to the teaching of H. T. Clarke et al.Org. Synth., Coll. Vol. 1, 2nd Ed. 1941, p. 85. Other benzenesulfonylchlorides are best made by diazotization of the appropriate aniline withsodium nitrite in HCl, followed by reaction of the diazonium salt withsulfur dioxide and cuprous chloride in acetic acid according to theteaching of H. L. Yale and F. Sowinski, J. Org. Chem., 25, 1824 (1960).

Substituted benzenesulfonyl chlorides containing an ortho α-haloalkylgroup can be made by methods known in the art. α-Chloroalkyl- anddichloromethylbenzenesulfonyl chlorides can be made by contacting thecorresponding alkylbenzenesulfonyl chlorides with with dichlorinemonoxide in an inert solvent, most conveniently in the temperature range40°-80°. The degree of chlorination is determined by the relativequantity of dichlorine monoxide employed, (Equation 7). (F. D. Marsh,U.S. Pat. No. 4,226,783 issued Oct. 7, 1980). ##STR16##

A series of standard functional group transformations may also be usedas described (J. F. King, A. Hawson, B. L. Huston, L. J. Danks, and J.Komery, Can. J. Chem., 49, 943 (1971) for2-(chloromethyl)benzenesulfonyl chloride (Equation 8). ##STR17##

Benzylic bromination using N-bromosuccinimide is useful in thepreparation of α-bromoalkylbenzenesulfonyl chlorides (Equation 9).##STR18## [W. B. Renfrow and M. Devadoss, J. Org. Chem., 40, 1525(1975)].

α-Fluoroalkyl substituted derivatives can be prepared by substitutingfluorine for chlorine. Thus an o-alkylnitrobenzene can be chlorinated(or dichlorinated) by the method of F. D. Marsh (op. cit.). These can beconverted to the corresponding fluoro derivatives according to methodssuch as described in "Aromatic Fluorine Compounds" A. E. Panlath and A.J. Teffler, Reinhold Publ. Co., New York (1962) or W. J. Middleton U.S.Pat. No. 3,940,402, issued Feb. 24, 1976, as shown by Equation 9awherein R, R₁, and R₂ are as previously defined. ##STR19## Conversion ofthe nitrobenzene derivative, obtained according to Equation 9a, toanilines can be carried out by a variety of methods (c.f. Compendium ofOrganic Synthetic Methods II, page 104, I. T. Harrison and S. Harrison,J. Wiley and Sons, New York, 1974) and these can be converted to thecorresponding sulfonyl chlorides by the method of H. L. Yale and F.Sowinski (op. cit).

The synthesis of heterocyclic amine derivatives has been reviewed in"The Chemistry of Heterocyclic Compounds," a series published byInterscience Publ., New York and London. 2-Aminopyrimidines aredescribed by D. J. Brown in "The Pyrimidines," Vol. XVI of the aboveseries.

2-Amino-1,3,5-triazines can be synthesized according to the methodsdescribed by E. M. Smolin and L. Rapaport in "s-Triazines andDerivatives," Vol. XIII of the same series.

The preparation of fused ring pyrimidine amines is disclosed inunexamined European Pat. No. 15683.

Compounds of Formula I can also be prepared by the method described inEquation 10 where Z is CH or N and R, R₁ and R₂ are as previouslydefined, provided that when L is NR₃ R₄ or NR₃ R₄ R₄ then R₃ or R₄cannot be H. ##STR20## wherein R, R₁ and R₂ are as described in Equation1;

L is as defined for Formula II;

Z is CH or N; and

R₉ is C₁ -C₃ alkyl.

Reaction Step 10a

In Reaction Step 10a an aromatic sulfonamide of Formula III iscontracted with a heterocyclic isocyanate of Formula VI to yield anN-(haloheterocyclicaminocarbonyl)aromatic sulfonamide of Formula II.

The heterocyclic isocyanates used in Reaction (10a) may be preparedaccording to methods described in Swiss Pat. No. 579,062, U.S. Pat. Nos.3,919,228, 3,732,223 and Angew Chem. Int. Ed., 10, 402 (1976), thedisclosures of which are herein incorporated by reference.

The aromatic sulfonamide and the heterocyclic isocyanate are contactedin the presence of an inert organic solvent, for example, acetonitrile,tetrahydrofuran (THF), toluene, acetone or butanone. Optionally, acatalytic amount of a base, such as 1,4-diazabicyclo[2.2.2]octane(DABCO), potassium carbonate, sodium hydride or potassium tert-butoxide,may be added to the reaction mixture. The quantity of base constitutinga catalytic amount would be obvious to one skilled in the art. Thereaction mixture is preferably maintained at a temperature of about 25°to 110° C., and the product can generally be recovered by cooling andfiltering the reaction mixture. For reasons of efficiency and economy,the preferred solvents are acetonitrile and THF, and the preferredtemperature range is about 60° to 85° C.

Reaction Steps 10b and 10c

In Reaction Steps 10b and 10c, one or two of the chlorine atoms on theheterocyclic ring of the compound of Formula II is displaced by anucleophilic species. Generally, this may be done by contacting thecompound of Formula II either with alkanol, R₉ OH, or with alkoxide,--OR₉, where R₉ is as defined above.

Thus, in Reaction Step (10b), a compound of Formula II can be contactedwith at least one equivalent of alkanol, R₉ OH. This reaction issluggish, however, and it is preferred to contact the compound ofFormula II with at least two equivalents of alkoxide, --OR₉. Thealkoxide can be provided in a number of ways:

(a) The compound of Formula II can be suspended or dissolved in analkanol solvent, R₉ OH, in the presence of at least two equivalents ofalkoxide, --OR₉. The alkoxide can be added directly as alkali metal oralkaline earth metal alkoxide or can be generated by the addition to thealkanol solvent of at least two equivalents of a base capable ofgenerating alkoxide from the solvent. Suitable bases include, but arenot limited to, the alkali and alkaline earth metals, their hydrides andtert-butoxides. For example, when R₉ is methyl, the compound of FormulaII could be suspended or dissolved in methanol in the presence of twoequivalents of sodium methoxide.

(b) Alternatively, two equivalents of sodium hydride could be used inplace of the sodium methoxide. The compound of Formula II can besuspended or dissolved in an inert solvent in the presence of at leasttwo equivalents of alkoxide, --OR₉. Suitable inert solvents include, butare not limited to, acetonitrile, THF and dimethylformamide. Thealkoxide may be added directly as alkali metal or alkaline earth metalalkoxide or may be generated from alkanol and a base as described in (a)above. For example, when R₉ is methyl, the compound of Formula II couldbe suspended or dissolved in THF in the presence of two equivalents ofsodium methoxide. Alternatively, two equivalents each of methanol andsodium hydride could be used instead of sodium methoxide.

For reasons of economy and efficiency, procedure (a) is the morepreferred method.

It should be noted that two equivalents of alkoxide are required forReaction Step (b) whereas only one equivalent of alkanol is needed forthe same process. This difference is due to the reaction which isbelieved to occur between the alkoxide and the sulfonyl nitrogen of thesulfonamide of Formula II. When alkoxide is used, the first equivalentof alkoxide removes a proton from the sulfonyl nitrogen, and is only thesecond equivalent which effects displacement of the halogen. As aresult, two equivalents of alkoxide are required. The resulting slatmust be acidified, i.e., with sulfuric, hydrochloric or acetic acid, toyield a compound of Formula VII. There is, of course, no intent to bebound by the mechanism described above.

In Reaction Step (10c), a compound of Formula VII substituted with atleast one displaceable group, is contacted with either one equivalent ofmethanol or with two equivalents of methoxide. The compound of FormulaVII is prepared according to Reaction Step (10b). from a compound ofFormula II.

When methoxide is used, it may be provided in either of the methodsdescribed above in connection with Reaction Step (10b) and the resultingsalt can be acidified to yield a compound of Formula IX.

When R₉ =CH₃, Reaction Steps (10b) and (10c) may be combined. Thus, acompound of Formula II may be contacted either with at least twoequivalents of methanol or with at least three equivalents of methoxide.

For a compound of Formula II, certain reaction conditions will favordisplacement of only one of the chlorine groups. These conditions arethe use of low temperatures and, when alkoxide is used, the slowaddition of the stoichiometric amount of alkoxide or alkoxide-generatingbase to the medium containing the compound of Formula VII.

When alkoxide is used, both Reaction Steps (10b) and (10c) arepreferably run at temperatures within the range of about 31 10° C. to80° C., the range of about 0° to 25° C. being more preferred. ReactionSteps (10b) and (10c) are more sluggish when alkanol is used instead ofalkoxide, and more drastic conditions are required for the reaction togo to completion. Thus, higher temperatures, up to and including theboiling point of the alkanol itself, are required.

As shown in Equation 11, compounds of Formula I, wherein A, R, R₁ and R₂are as previously defined, provided that when L is NR₃ R₄ or NR₃ R₄ R₄ 'then R₃ or R₄ cannot be H, are prepared by the reaction of anappropriately substituted sulfonamide (III) with the appropriateheterocyclic isothiocyanate of Formula X. ##STR21## The reaction ofEquation 11 is best carried out by dissolving or suspending thesulfonamide and isothiocycante in a polar solvent such as acetone,acetonitrile, ethyl acetate or methylethylketone, adding an equivalentof a base such as potassium carbonate and stirring the mixture atambient temperature up to the reflux temperature for one to twenty-fourhours. In some cases, the product precipitates from the reaction mixtureand can be removed by filtration. The product is stirred in dilutemineral acid, filtered and washed with cold water. If the product doesnot precipitate from the reaction mixture it can be isolated byevaporation of the solvent, trituration of the residue with diluteminteral acid and filtering off the insoluble product.

The heterocyclic isothiocyanates which are used in the procedure ofEquation 11 are prepared, for example, according to the method of Japanpatent Application Pub: Kokai 51-143686, June 5, 1976, or that of W.Abraham and G. Barnikow Tetrahedron 29, 691-7 (1973).

The disclosures of all references cited above are herein incorporated byreference.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides and can be prepared by a number of ways known to the art. Forexample, metal salts can be made by treating compounds of Formula I witha solution of alkali or alkaline earth metal salt having a sufficientlybasic anion (e.g., hydroxide, alkoxide, carbonate or hydride).Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of onecation for another. Cationic exchange can be effected by directtreatment of an aqueous solution of a salt of a compound of Formula I(e.g., alkali metal or quaternary amine salt) with a solution containingthe cation to be exchanged. This method is most effective when thedesired salt containing the exchanged cation is insoluble in water,e.g., a copper salt, and can be separated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of Formula I (e.g., an alkali metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged. In this method, the cation of the resin isexchanged for that of the original salt and the desired product iseluted from the column. This method is particularly useful when thedesired salt is water soluble, e.g., a potassium, sodium or calciumsalt.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of Formula I with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like. One suchaddition salt is described in Examples 8 and 9.

The 2-(1-haloalkyl)benzenesulfonyl ureas are also useful precursors toother herbicidal sulfonyl ureas of this invention: ##STR22## R, R₂, Aare as above with the proviso that X,Y,Y'≠Cl, Br R₁ '=H, C₁ -C₄ alkyl

The above reaction is conveniently carried out in a solvent such asdimethylformamide or acetonitrile. Details are provided in Examples 8and 9.

EXAMPLE 12-(Dichloromethyl)-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide##STR23##

o-Dichloromethylbenzenesulfonamido (2.40 g, 10 mmol) was treated withthionyl chloride (25 ml) and heated to reflux for 16 hrs. Volatiles wereremoved under vacuum and the residue was treated with thionyl chloride(20 ml) and refluxed for 22 hrs. Thionyl chloride was removed undervacuum, and two portions of dry toluene were added and evaporated inorder to remove last traces of SOCl₂. The crude product in toluene (45ml) was transferred to a threeneck flask, treated with dry pyridine (1.0ml), and then treated slowly with phosgene such that a slow reflux wasmaintained while the internal temperature was held at ca. 70° for 1.0hr. Excess phosgene was removed using a stream of dry nitrogen. IR ofthe crude residue showed only a trace NH stretch and featured a strongband at 2250 cm⁻¹.

The crude isocyanate in dry acetonitrile (15 ml) was treated with2-amino-4-methoxy-6-methyl pyrimidine (1.39 g, 10 mmol). The aminedissolved and a precipitate formed. The mixture was stirred for 16 hrs,filtered, and the solid was washed with ca. 3 ml acetonitrile to give1.51 g of off-white solid, mp 183°-185° C. ¹ H nmr:δ_(DMSO-d).sbsb.6^(TMS) 10.3 (brd s, NH), 8.25-7.58 (m, featuringsinglet at 8.13), 6.62 (s) 3.98 (s), 2.42 (s). Recrystallization fromCHCl₃ gave 0.89 g, mp 189°-190° (dec.). Mass spec: measured 404.0083;calc'd for C₁₄ H₁₄ N₄ O₄ SCl₂ 404.0110.

Anal. Calc'd: C, 41.49; H, 3.48; N, 13.83, Found: C, 41.22; H, 3.21; N,13.83, C, 41.12 H, 3.50 N, 13.67.

EXAMPLE 22-(Dichloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide##STR24##

2-(Dichloromethyl)benzenesulfonyl isocyanate, prepared from 10 mmol ofsulfonamide as described in the synthesis of Example 1, was treated withacetonitrile and 2-amino-4,6-dimethylpyrimidine (1.23 g). The mixturewas stirred at room temperature for 18 hrs, cooled, and filtered toprovide 1.08 g of white solid, mp 195°-197° (Dec). ¹ H nmrδ_(CDCl).sbsb.3_(/DMSO-d).sbsb.6^(TMS) 10.53 (s), 8.20-7.90 (m,featuring singlet at 8.00), 7.87-7.43 (m), 6.83 (s), 2.43 (s). IR(nujol) featured bands at 1710 and 1600 cm⁻¹. Mass spectrum featured m/e388.0174 (calc'd for C₁₄ H₁₄ Cl₂ N₄ O₃ S 388.0163); 150.0627 (calc'd forC₇ H₇ N₃ 150.0667).

EXAMPLE 32-(Dichloromethyl)-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide##STR25##

2-(Dichloromethyl)benzenesulfonyl isocyanate prepared from 10 mmol ofsulfonamide as described in the synthesis of Example 1, was treated withacetonitrile (15 ml) and 2-amino-4-methoxy-6-methyl-1,3,5-triazine (1.40g). The mixture was stirred for 18 hrs. and filtered. The filtrate wasevaporated and recrystallized from acetone to give 0.78 g of whitesolid, mp. 168°-169° (dec). ¹ H nmr δ_(DMSO-d).sbsb.6^(TMS) 8.37-7.50(m, featuring singlet at 8.07), 7.00-6.17 (brds), 4.00 (s), 2.48 (s). IR(nujol) featured bands at 1720 and 1590 cm⁻¹. Mass spectrum featured264.9367 (calc'd for C₈ H₅ Cl₂ NO₃ S 264.9367) and 140.0687 (calc'd forC₅ H₈ N₄ O 140.0697).

Anal. Calc'd: C, 38.44; H, 3.23; N, 17.24, Found: C, 38.74; H, 3.13; N,16.90, C, 38.59; H, 3.11 N, 17.04.

EXAMPLE 42-(Chloromethyl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide##STR26##

A solution of 4,6-dichloro-1,3,5-triazin-2-yl isocyanate (3.10 g, 16.2mmol) in acetonitrile (15 ml) was contacted with 2-(chloromethyl)benzenesulfonamide (3.34 g, 16.2 mmol) and stirred for 20 hrs at 25°. Themixture was heated at 50° for 2 hrs, cooled and filtered to provide 3.86g, mp 162°-170°, which was contacted with sodium methoxide (30 mmol) inmethanol (60 ml) at 20°-25°for 16 hrs. Water (100 ml) was added and themixture was filtered and neutralized by addition of hydrochloric acid.Filtration and drying gave 2.20 g of white solid, mp 150°-152° (dec.). ¹H nmr δ_(DMSO-d).sbsb.6^(TMS) 11.0 (s), 8.30-7.50 (m), 5.23 (s), 4.03(s). IR (nujol) featured absorption bands centered at 3200, 1720, 1610and 1560 cm⁻¹.

Anal. Calc'd for C₁₃ H₁₄ N₅ ClO₅ S C, 40.26; H, 3.64; N, 18.06. Found C,38.60; H, 3.62; N, 18.40.

EXAMPLE 52-(Chloromethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide##STR27##

A solution of 2-(chloromethyl)-N-(butylaminocarbonyl)benzene sulfonamide(1.33 g, 4.38 mmol) and diazabicyclo[2.2.2]octane (5 mg) in xylene (12ml) was heated at reflux and contacted in portions with phosgene (1.0ml. condensed phase). After 2.0 hrs at reflux, the mixture was cooled toroom temperature, decanted, and volatiles were removed to give 1.56 g ofcrude product. The IR spectrum of 2-(chloromethyl)-benzenesulfonylisocyanate featured a strong band at 2250 cm⁻¹. The crude sulfonylisocyanate was contacted with acetonitrile (10 ml) and2-amino-4,6-dimethoxypyrimidine (0.68 g, 4.4 mmol) and stirred for 16hrs. Filtration gave 1.18 g of white solid, mp 192°-193°. The sample wasdissolved in 0.5N NaOH, filtered and pH adjusted to 6.5. The mixture wascooled and filtered and the solid washed with ice water and dried togive 0.90 g of white solid. ¹ H nmr δ_(DMSO-d).sbsb.6^(TMS) 12.7 (brd s,10.50 (s, 1H) 8.13-7.97 (m, 1H), 7.73-7.40 (m, 3H), 5.90 (s, 1H), 5.10(s, 2H), 3.87 (s, 6H).

Anal. Calc'd: C, 43.47; H, 3.91; N, 14.48; S, 8.29 Found: C, 41.76; H,3.82; N, 13.94; S, 8.23.

EXAMPLE 62-(Chloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide##STR28##

A mixture of 2-(chloromethyl)benzene sulfonamide (4.11 g, 20 mmol) andthionyl chloride (35 ml) was heated to reflux for 36 hrs. Thionylchloride was removed under vacuum. The residue was contacted withtoluene (100 ml) and pyridine (2 ml), heated to 70°, and treated inportions with phosgene (excess) for 2.0 hrs. The mixture was cooled, andthe toluene-soluble portion was decanted and evaporated to give aresidue which was treated with acetonitrile (15 ml) and2-amino-4,6-dimethylpyrimidine (1.70 g, 13.8 mmol). After 16 hrs, thesolid was filtered and washed with acetonitrile to give 1.45 g of solidwhich was taken up in 1.0N NaOH and filtered. The pH was adjusted to 6.0with dilute hydrochloric acid and the solid was filtered and dried toprovide 1.34 g of creamcolored solid, mp 176°-177° (dec.). IR (KBr)featured absorption bands at 3340-2300,1700 (strong), 1600, 1500, 1440,1340 cm⁻¹.

EXAMPLE 72-(1-Chloroethyl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide##STR29##

A solution of 4,6-dichloro-1,3,5-triazin-2-yl isocyanate (2.27 g, 11.9mmol) in acetonitrile (20 ml) was contacted with2-(1-chloroethyl)benzenesulfonamide (2.61 g, 11.9 mmol) and stirred at25° for 18 hrs. and at 50° for 2.0 hrs. Solvent was evaporated to give4.95 g of residue. ¹ H nmr δ_(CDCl).sbsb.3^(TMS) 11.35 (s), 8.87 (s),8.33-7.30 (m), 6.18 (q, J=7 Hz), 5.50 (s), 1.88 (d, J=7 Hz). MassSpectrum: observed 244.9915 (calc'd for C₉ H₈ O₃ NClS 244.9913),163.9643 (calc'd for C₃ H₂ N₄ Cl₂ 163.9656).

A solution of the above sulfonyl urea in methanol (20 ml) was contactedwith a solution of sodium methoxide (36 mmol) in methanol (65 ml) at 0°for 3.0 hrs. Solvent was evaporated and the residue was taken up inwater (120 ml), filtered, and pH was brought to 5.0 g with dilute HCl.The mixture was cooled and filtered and the solid was washed with thewater and dried to give 3.52 g of white solid, mp 148°-150° (dec.). ¹ Hnmr δ.sub.(CD.sbsb.3.sub.).sbsb.2_(CO) ^(TMS) 8.30-7.42 (m), 6.32 (q,J=7 Hz), 4.08 (s), 2.93 (brds), 1.88 (d, J=7 Hz).

Mass spectrum showed: 244.9912 (calc'd for C₉ H₈ O₃ NClS 244.9913)156.0616 (calc'd for C₅ H₈ O₂ N₄ 156.0647)

Anal. Calc'd: C, 41.85; H, 4.01; N, 17.43, Found: C, 41.92; H, 4.05; N,17.02.

EXAMPLE 82-(1-Pyrrolidinylmethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide,hydrochloride salt ##STR30##

A slurry of2-(chloromethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide(1.00 g) in dimethylformamide (5 ml) was contacted with pyrrolidine(0.45 ml) and stirred for 3.5 hrs. Volatiles were removed under vacuumand the residue was taken up in methanol. Solvent was removed and thewater (15 ml) was added and the pH was adjusted to 6.0 by addition ofdilute hydrochloric acid. Cooling and scratching produced a white solidwhich was collected and dried to give 488 mg, m.p. 117°-123°. A 400 mgsample was crystallized from acetonitrile to give 269 mg. m.p. 132°-134°C. ¹ H nmr δ_(CDCl).sbsb.3^(TMS) 13.0-11.0 (brds 2H), 8.63 (s, 1 NH),8.37-8.20, 8.05-7.90, and 7.70-7.33 (m, 4H), 5.68 (s, 1H), 5.00 (s, 2H),3.90 (s, 6H), 3.70-2.90 (m, 4H), 2.30-1.90 (m, 4H). IR (KBr) 3650-2200,1710, 1610, 1580, 1450, 1360, 1200, 1165 are major absorption bands.

Anal. Found C, 44.99; H, 5.17; N, 14.56 Calc'd for C₁₈ H₂₃ N₅ O₅ S.HClC, 47.21; H, 5.28; N, 15.30

EXAMPLE 9 2-(1-Pyrrolidinylmethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide ##STR31##

A slurry of2-(chloromethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide(1.00 g) is dimethylformamide (5 ml) was contacted with pyrrolidine(0.45 ml) and stirred for 2.5 hrs. Volatiles were removed under vacuumand the residue was washed several times with ether, taken up inmethanol and treated dropwise with a ca. 0.5% solution of dryhydrochloric acid in methanol to adjust the apparent pH to 6.5-7.0.Volatiles were again removed to provide 1.34 g. of glassy foam whichwere chromatographed on silica gel eluting with 2/1 ethylacetate/methanol. Residues from the major fractions were taken up inwarm chloroform and evaporated. Addition of a small volume ofacetonitrile yielded, upon cooling and scratching, a total of 280 mg ofwhite solid, up 138°-140° (dec). ¹ H nmr δ_(CDCl).sbsb.3^(TMS) 8.10-7.90(m, 1H), 7.67-7.10 (m, 4H, featuring NH singlet at 7.57), 5.50 (s, 1H),4.60 (s, 2H), 3.72 (s, 6H), 3.43-3.10 (m, 4H), 2.30-1.90 (m, 4H). IR(KBr) 3680-2300, 1660, 1600, 1450, 1370, 1280, 1150, and 1110 cm⁻¹ weremajor absorption bands.

Anal. Calc'd for C₁₈ H₂₃ N₅ O₅ S C, 51.29; H, 5.50; N, 16.62, Found: C,50.40; H, 5,29; N, 15.86.

Contacting a CDCl₃ solution of the above compound with dry hydrochloricacid produced the same substance described in Example 8 as judged by ¹ Hnmr and IR spectral data.

EXAMPLE 10 2-(1-Chloroethyl)benzenesulfonyl chloride ##STR32##

A solution of 2-ethylbenzenesulfonyl chloride (obtained bychlorosulfonation of ethylbenzene) (7.78 g) in carbon tetrachloride (5.0ml) was contacted with a solution of dichlorine monoxide (82 mmol) incarbon tetrachloride (100 ml) and the mixture was heated in a closedsystem at 50°-60° for 16 hrs. The mixture was dried (MgSO₄) andvolatiles were removed under vacuum. The residue was kugelrohr distilledto give 7.63 g of colorless oil, bp 75°-80° (0.15 mm). ¹ H nmrδ_(CDCl).sbsb.3^(TMS) 8.20-7.35 (m). 6.13 (g, J-7 Hz), 1.90 (d, J=7 Hz).

EXAMPLE 11 2-Dichloromethylbenzene sulfonamide ##STR33##

A solution of o-methylbenzenesulfonyl chloride (7.97 g, 42 mmol) in CCl₄(10 ml) was contacted with a solution of Cl₂ O in CCl₄ (108 ml, 96 mmol)and the mixture was heated at 50° for 23 hrs. The cooled solution waspurged with a stream of nitrogen, dried (MgSO₄), and evaporated to give10.1 g of white solid. ¹ H nmr: 8.43-7.47 (m, featuring a singlet at7.82).

The product sulfonyl chloride was dissolved in tetrahydrofuran (50 ml)and was added to a solution of ammonia (2.7 ml at -78°) intetrahydrofuran (100 ml) at -78°. The mixture was allowed to warm slowlyto 5°. Solvent was removed under vacuum, and the residue was taken up inCH₂ Cl₂, washed with water, dried, and evaporated to give 8.3 g ofsolid. Recrystallization from CHCl₃ gave 5.34 g of shiny plates, m.p.131°-132°. ¹ H nmr δ_(acetone-d).sbsb.6^(TMS) 8.33-7.47 (m. featuring sat 8.00), 7.30-6.87 (brds). Mass spec: measured 238.9560. Calc'd. for C₇H₇ Cl₂ NO₂ S, 238.9574.

EXAMPLE 12 2-(Bromomethyl)benzenesulfonyl chloride ##STR34##

A solution of toluenesulfonyl chloride (4.5 g, ca. 85/15 mixture ofortho/para isomers) in carbon tetrachloride (40 ml) was contacted withN-bromosuccinimide (4.3 g) and azobisisobutyronitrile (50 mg) and heatedto reflux for 22 hrs. The cooled mixture was filtered and the solventwas evaporated to give 6.33 g of yellow oil. Kugelrohr distillationprovided 4.31 g, b.p. 90°-98° (0.2 mm). ¹ H nmr δ_(CDCl).sbsb.3^(TMS)8.46-7.25 (m), 5.0 (s, area 47), 4.58 (s, area 12), 2.76 and 2.47(singlets for unchanged toluenesulfonyl chloride contaminant). Theortho/para ratio of bromomethyl compounds was 80/20.

EXAMPLE 13 2-(Hydroxymethyl)benezenesulfonic acid, sodium salt ##STR35##

A solution of o-benzaldehydesulfonic acid, sodium salt (120 g) in water(2 l) was contacted in portions with sodium borohydride (21.6 g) and thesolution was stirred for 48 hrs. The pH of the solution was adjusted to7.0 by addition of hydrochloric acid. Water was removed under reducedpressure, and the residue was added to a large thimble and continuouslyextracted with ethanol. Concentration and cooling provided 102 g. ofwhite solid, m.p. >300°. Evaporation of the mother liquor gave anadditional 13.4 g of product. ¹ H nmr δ_(D).sbsb.2_(O) ^(DSS) 8.10-7.85(m), 7.77-7.26 (m). 5.13 (s), 4.70 (s).

EXAMPLE 14 2-Chloromethyl)benzenesulfonyl chloride ##STR36##

2-(Hydroxymethyl)benzenesulfonic acid, sodium salt (76 g) was contactedwith phosphorus oxychloride (375 ml) and the stirred mixture was treatedin portions with phosphorus pentachloride (76 g). The mixture was heatedat 60°-70° for two days. Phosphorus oxychloride was removed under vacuumand the residue was treated with toluene (700 ml) and decanted intowater. The organic layer was washed with water and brine, dried (MgSO₄)and evaporated. The product was kugelrohr distilled 90°-100°, 0.2 mm) togive 56 of white solid, m.p. 43°-45°. ¹ H nmr: δ_(COCl).sbsb.3^(TMS)8.17-8.00 (m), 7.90-7.40 (m), 5.10 (s).

EXAMPLE 15 2-(Chloromethyl)benzenesulfonamide ##STR37##

A solution of ammonia (5.2 ml) in tetrahydrofuran (250 ml) at -70° wascontacted rapidly with a solution of 2-(chloromethyl)benzenesulfonylchloride (21.8 g) in tetrahydrofuran (125 ml). The stirred mixture wasallowed to warm to 0° and volatiles were removed under vacuum. Theresidue was contacted with ethyl acetate and a small volume of water.The organic layer was dried (MgSO₄) and evaporated to give 19.8 g ofwhite solid, m.p. 156°-157.5°. Recrystallization from toluene/ethylacetate gave a sample with m.p. 157°-160°. ¹ H nmrδ.sub.(CD.sbsb.3.sub.).sbsb.2_(CO) ^(TMS) 8.16-7.35 (m), 6.75 brds),5.20 (s), 3.08 (s).

EXAMPLE 16 2-(1-Chloroethyl)benzenesulfonamide ##STR38##

A solution of ammonia (1.2 ml) in tetrahydrofuran (100 ml) at -70° wascontacted rapidly with a solution of 2-(1-chloroethyl)benzenesulfonylchloride (4.32 g, 18.1 mmol) in tetrahydrofuran (50 ml). The stirredmixture was allowed to warm to 0° and volatiles were removed underreduced pressure. The residue was taken up in ethyl acetate and washedwith a small volume of water and brine. The dried (MgSO₄) solution wasevaporated to give 4.7 g of off white solid which was recrystallizedfrom chloroform to give 3.13 g, m.p. 121°-122°. ¹ H nmrδ.sub.(CD.sbsb.3.sub.).sbsb.2_(CO) ^(TMS) 8.25-7.30 (m), 6.93 (brds),6.25 (q, J=7 Hz), 3.17 (s), 1.98 (d, J=7 Hz).

EXAMPLE 17 2-(Bromomethyl)benzenesulfonamide ##STR39##

A solution of ammonia (1.0 ml) in tetrahydrofuran (50 ml) at -78° wascontacted dropwise with a solution of a 60/40 mixture of2-(bromomethyl)benzenesulfonyl chloride/4-(bromomethyl)benzenesulfonylchloride (4.52 g) in tetrahydrofuran (20 ml). The stirred mixture wasallowed to warm to 0° and volatiles were removed in vacuo. The residuewas contacted with water (50 ml) and extracted three times with ethylacetate. Combined organic portions were washed with brine, dried, andevaporated to give 4.00 g of white solid. ¹ H nmrδ.sub.(CD.sbsb.3.sub.).sbsb.2_(CO) ^(TMS) 8.15-7.20 (m), 6.7-6.3 (m,NH), 4.95 (q, area 21), 4.55 (s, area 18), consistent with a ca. 60/40mixture of 2-(bromomethyl)-/4-(bromomethyl)-benzenesulfonamides. Thesample was fractionally recrystallized from chloroform, but withoutsignificant change in isomeric content.

EXAMPLE 18 2-(1-Pyrrolidinylmethyl)benzenesulfonamide ##STR40##

A solution of 2-(chloromethyl)benzenesulfonamide (2.00 g, 10 mmol) inacetonitrile (20 ml) was contacted with pyrrolidine (1.6 ml, 20 mmol).After 1.0 hr at ambient temperature, the volatiles were removed undervacuum and the residue was treated with water (40 ml) and chilled. Theresulting solid was pulverized, filtered, and dried to give 2.23 g ofwhite solid, m.p. 110°-112°.

Anal. Found C, 55.14; H, 6.71; N, 11.40; C, 54.66; H,, 6.49; N, 11.49;Calc'd for C₁₁ H₁₆ N₂ O₂ S: C, 54.97; H, 6.71; N, 11.66.

EXAMPLE 19 2-(1-Pyrrolidinylmethyl)benzenesulfonamide, methyl iodidesalt. ##STR41##

A solution of 2-(pyrrolidinomethyl)benzenesulfonamide (0.8 g) inacetonitrile (10 ml) was contacted with methyl iodide (3 ml) and heatedto reflux for 2.0 hrs. Solvent was removed and the residue was treatedwith acetone and ether. The solid was filtered, digested with acetone(20 ml), chilled, and collected. There was obtained 1.00 g of whitesolid. ¹ H nmr δ_(DMSO-d).sbsb.6^(TMS) 8.15-7.30 (m), 5.07 (s, 2H),3.9-3.3 (m, 4H), 2.90 (s, 3H), 2.4-1.8 (m 4H).

EXAMPLE 20 2-(Chloromethyl)-N-(butylaminocarbonyl)benzenesulfonamide##STR42##

A mixture of 2-(chloromethyl)benzenesulfonamide (13.2 g, 64 mmol) andbutyl isocyanate (7.0 g, 71 mmol) in xylene (80 ml) was contacted withdiazabicyclo[2.2.2]-octane (0.25 g) and heated to reflux for 5.0 hrs.Volatiles were removed under vacuum and the residue was treated with0.5N NaOH (200 ml) and extracted with ethyl acetate (75 ml). The aqueouslayer was separated, chilled, acidified (pH 4) with hydrochloric acid,and extracted with ethyl acetate. The organic layer was washed withbrine, dried (MgSO₄), and evaporated to give 14.6 g of white solid. Asample was recrystallized from toluene to give m.p. 104°-106°. ¹ H nmrδ_(CDCl).sbsb.3^(TMS) 9.5-8.1 (brds), 8.05-7.10 (m), 6.28 (t, J=2 Hz),4.91 (s), 3.25-2.95 (m), 1.70-0.70 (m).

Examplary compounds within structure I that can be made by one or moreof the described methods (Examples 1-9) are listed in Table I and II.

                                      TABLE I                                     __________________________________________________________________________     ##STR43##                                                                    L            R       R.sub.1                                                                              R.sub.2                                                                          X   Y     Z         m.p.                       __________________________________________________________________________                                                       (°C.)               Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH        176-177°            Br           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR44##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR45##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR46##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR47##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR48##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR49##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR50##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR51##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR52##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR53##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR54##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR55##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR56##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR57##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   N(CH.sub.3).sub.2                                                                          H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   N(CH.sub.3)(C.sub.2 H.sub.5)                                                               H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   N(C.sub.2 H.sub.5).sub.2                                                                   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   N(C.sub.3 H.sub.7).sub.2                                                                   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR58##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR59##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   N(OCH.sub.3)CH.sub.3                                                                       H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   NH.sub.2     H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   NHCH.sub.3   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   F            H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   F            H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    F            H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   F            H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    F            H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   F            H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    F            H       H      H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                  CH                                   F            H       H      H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  N                                    F            H       H      H  Cl  OCH.sub.3                                                                           CH                                   Cl           H       H      H  CH.sub.3                                                                          Cl    CH                                   Br           H       H      H  CH.sub.3                                                                          Cl    CH                                    ##STR60##   H       H      H  CH.sub.3                                                                          Cl    CH                                    ##STR61##   H       H      H  CH.sub.3                                                                          Cl    CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  CH.sub.3                                                                          Cl    CH                                    ##STR62##   H       H      H  CH.sub.3                                                                          Cl    CH                                   F            H       F      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   F            H       F      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   F            H       F      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   F            H       F      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    F            H       F      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    F            H       F      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    F            H       F      H  Cl  OCH.sub.3                                                                           CH                                   NHC.sub.4 H.sub.9                                                                          H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   N(CH.sub.3)(n-C.sub.4 H.sub.9)                                                             H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR63##   H       H      H  CH.sub.3                                                                          CH.sub. 3                                                                           CH                                    ##STR64##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR65##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR66##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR67##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR68##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR69##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR70##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR71##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR72##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR73##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR74##   H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           H       CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           H       CH.sub.2 CH.sub.2 CH.sub.3                                                           H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           H       n-C.sub.4 H.sub.9                                                                    H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CCl                                  Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CBr                                  Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CCN                                  Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CCH.sub.3                            Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CCH.sub.2 CH.sub.3                   Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CCH.sub.2 CH.sub.2 Cl                Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            CCH.sub.2 CHCH.sub.2                 Cl           5-F     H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-Br    H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-CH.sub.3                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-CH.sub.2 CH.sub.2 CH.sub.3                                                          H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-OCH.sub.3                                                                           H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-OCH(CH.sub.3).sub.2                                                                 H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           CF.sub.3                                                                              H      H  CH.sub.3                                                                          CH.sub. 3                                                                           CH                                   Cl           H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   Br           H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR75##   H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR76##   H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR77##   H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   Cl           H       H      H  H   CH.sub.3                                                                            CH                                   Br           H       H      H  H   CH.sub.3                                                                            CH                                    ##STR78##   H       H      H  H   CH.sub.3                                                                            CH                                    ##STR79##   H       H      H  H   CH.sub.3                                                                            CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  H   CH.sub.3                                                                            CH                                    ##STR80##   H       H      H  H   CH.sub.3                                                                            CH                                   Cl           H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Br           H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR81##   H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR82##   H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR83##   H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   Br           H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR84##   H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR85##   H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR86##   H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   Cl           H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH        192-193°            Br           H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR87##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH        138-140°             ##STR88##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR89##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR90##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR91##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR92##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR93##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR94##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR95##   H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Cl           H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Br           H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR96##   H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR97##   H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR98##   H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Cl           5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Br           5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR99##   5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR100##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR101##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Br           5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR102##  5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR103##  5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                    ##STR104##  5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   Br           5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR105##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR106##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR107##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   Cl           5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   Br           5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR108##  5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR109##  5-Cl    H      H  CH.sub. 3                                                                         OCH.sub.3                                                                           CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                    ##STR110##  5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                   Cl           5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Br           5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR111##  5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR112##  5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR113##  5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Cl           5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Br           5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR114##  5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR115##  5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   .sup.⊕N(CH.sub.3).sub.3                                                                5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                    ##STR116##  5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Cl           H       Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            CH        195-197°            Br           H       Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           H       Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            CH        189-190°            Cl           H       Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Br           H       Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                   Br           H       Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Cl           5-Cl    Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-NO.sub.2                                                                            Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Br           5-Cl    Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Br           5-NO.sub.2                                                                            Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                   Cl           5-Cl    Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                   Cl           5-NO.sub.2                                                                            Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                   Br           5-Cl    Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Br           5-NO.sub.2                                                                            Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Cl           5-Cl    Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Cl           5-NO.sub.2                                                                            Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                   Br           5-Cl    Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                   Br           5-NO.sub.2                                                                            Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                   Cl           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Br           H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR117##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR118##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR119##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR120##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR121##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR122##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR123##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR124##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR125##  H       H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Cl           H       H      H  CH.sub.3                                                                          Cl    N                                    Br           H       H      H  CH.sub.3                                                                          Cl    N                                     ##STR126##  H       H      H  CH.sub.3                                                                          Cl    N                                     ##STR127##  H       H      H  CH.sub.3                                                                          Cl    N                                    .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  CH.sub.3                                                                          Cl    N                                     ##STR128##  H       H      H  CH.sub.3                                                                          Cl    N                                    Cl           H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    Br           H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR129##  H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR130##  H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR131##  H       H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    Cl           H       H      H  H   CH.sub.3                                                                            N                                    Br           H       H      H  H   CH.sub.3                                                                            N                                     ##STR132##  H       H      H  H   CH.sub.3                                                                            N                                     ##STR133##  H       H      H  H   CH.sub.3                                                                            N                                    .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  H   CH.sub.3                                                                            N                                     ##STR134##  H       H      H  H   CH.sub.3                                                                            N                                    Cl           H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                    Br           H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR135##  H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR136##  H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                    .sup.⊕N(CH.sub.3).sub.3                                                                H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR137##  H       H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                    Cl           H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           N                                    Br           H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR138##  H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR139##  H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           N                                    .sup.⊕N(CH.sub.3).sub.3                                                                H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR140##  H       H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           N                                    Cl           H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N         150-152°            Br           H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR141##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR142##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    .sup.⊕N(CH.sub.3).sub.3                                                                H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR143##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR144##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR145##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR146##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR147##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR148##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR149##  H       H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Cl           H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N         148-150°            Br           H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR150##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR151##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    .sup.⊕N(CH.sub.3).sub.3                                                                H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR152##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR153##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR154##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR155##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR156##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR157##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR158##  H       H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Cl           5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Br           5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR159##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR160##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    .sup.⊕N(CH.sub.3).sub.3                                                                5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR161##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Cl           5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Br           5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR162##  5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR163##  5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    .sup.⊕N(CH.sub.3).sub.3                                                                5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                     ##STR164##  5-Cl    H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Cl           5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    Br           5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR165##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR166##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    .sup.⊕N(CH.sub.3).sub.3                                                                5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR167##  5-NO.sub.2                                                                            H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    Cl           5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    Br           5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR168##  5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR169##  5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    .sup.⊕N(CH.sub.3 ).sub.3                                                               5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                     ##STR170##  5-Cl    H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                    Cl           5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Br           5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR171##  5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR172##  5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    .sup.⊕N(CH.sub.3).sub.3                                                                5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR173##  5-NO.sub.2                                                                            H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Cl           5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Br           5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR174##  5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR175##  5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    .sup.⊕N(CH.sub.3).sub.3                                                                5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                     ##STR176##  5-Cl    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Cl           H       Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Br           H       Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Cl           H       Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            N         168-169°            Cl           H       Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Br           H       Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                    Br           H       Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Cl           5-Cl    Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Cl           5-NO.sub.2                                                                            Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Br           5-Cl    Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Br           5-NO.sub.2                                                                            Cl     H  CH.sub.3                                                                          CH.sub.3                                                                            N                                    Cl           5-Cl    Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                    Cl           5-NO.sub.2                                                                            Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                    Br           5-Cl    Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Br           5-NO.sub.2                                                                            Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Cl           5-Cl    Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Cl           5-NO.sub.2                                                                            Cl     H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                    Br           5-Cl    Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                    Br           5-NO.sub.2                                                                            Cl     H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                    __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                         ##STR177##                                                                                                              m.p.                               L         R R.sub.1  R.sub.2                                                                     R.sub.8 W   X     Y     Z (° C.)                    ______________________________________                                        Cl        H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            CH.sub.3                                                                            CH                                 Cl        H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           CH.sub.3                                                                            CH                                 Cl        H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                 Cl        H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            CH.sub.3                                                                            N                                  Cl        H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            OCH.sub.3                                                                           N                                  Cl        H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           N                                   ##STR178##                                                                             H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            CH.sub.3                                                                            CH                                  ##STR179##                                                                             H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           CH.sub.3                                                                            CH                                  ##STR180##                                                                             H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  ##STR181##                                                                             H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            CH.sub.3                                                                            N                                   ##STR182##                                                                             H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           CH.sub.3                                                                            N                                   ##STR183##                                                                             H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           N                                   ##STR184##                                                                             H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            CH.sub.3                                                                            CH                                  ##STR185##                                                                             H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            OCH.sub.3                                                                           CH                                  ##STR186##                                                                             H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  ##STR187##                                                                             H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            CH.sub.3                                                                            N                                   ##STR188##                                                                             H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           CH.sub.3                                                                            N                                   ##STR189##                                                                             H  HH    CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  N.sup.⊕ (CH.sub.3).sub.3                                                            H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  ##STR190##                                                                             H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                 Cl        H HH     H       S   CH.sub.3                                                                            CH.sub.3                                                                            CH                                 Cl        H HH     H       S   OCH.sub.3                                                                           CH.sub.3                                                                            CH                                 Cl        H HH     H       S   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                 Cl        H HH     H       S   OCH.sub.3                                                                           CH.sub.3                                                                            N                                  Cl        H HH     H       S   OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  Cl        H HH     OCH.sub.3                                                                             O   CH.sub.3                                                                            CH.sub.3                                                                            CH                                 Cl        H HH     OCH.sub.3                                                                             O   CH.sub.3                                                                            OCH.sub.3                                                                           CH                                 Cl        H HH     OCH.sub.3                                                                             O   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                 Cl        H HH     OCH.sub.3                                                                             O   CH.sub.3                                                                            CH.sub.3                                                                            N                                  Cl        H HH     OCH.sub.3                                                                             O   CH.sub.3                                                                            OCH.sub.3                                                                           N                                  Cl        H HH     OCH.sub.3                                                                             O   OCH.sub.3                                                                           OCH.sub.3                                                                           N                                   ##STR191##                                                                             H HH     OCH.sub.3                                                                             O   CH.sub.3                                                                            CH.sub.3                                                                            CH                                  ##STR192##                                                                             H HH     OCH.sub.3                                                                             O   CH.sub.3                                                                            OCH.sub.3                                                                           CH                                  ##STR193##                                                                             H HH     OCH.sub.3                                                                             O   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  ##STR194##                                                                             H HH     OCH.sub.3                                                                             O   CH.sub.3                                                                            CH.sub.3                                                                            N                                   ##STR195##                                                                             H HH     OCH.sub.3                                                                             O   CH.sub.3                                                                            OCH.sub.3                                                                           N                                   ##STR196##                                                                             H HH     OCH.sub.3                                                                             O   OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  F         H HH     CH.sub.3                                                                              O   CH.sub.3                                                                            OCH.sub.3                                                                           N                                  F         H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                 F         H HH     CH.sub.3                                                                              O   OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  ______________________________________                                    

                                      TABLE III                                   __________________________________________________________________________     ##STR197##                                                                   R      R.sub.1                                                                             R.sub.2                                                                          R.sub.8                                                                           Y'    Q  L                                                __________________________________________________________________________    H      H     H  H   CH.sub.3                                                                            O  Cl                                               H      H     H  H   CH.sub.3 O                                                                          O  Cl                                               H      H     H  H   Cl    O  Cl                                               H      H     H  H   H     O  Cl                                               H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         Cl                                               H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               H      Cl    H  H   CH.sub.3                                                                            O  Cl                                               H      Cl    H  H   CH.sub.3 O                                                                          O  Cl                                               H      Cl    H  H   Cl    O  Cl                                               H      Cl    H  H   H     O  Cl                                               H      Cl    H  H   CH.sub.3                                                                            CH.sub.2                                                                         Cl                                               H      Cl    H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               H      H     H  H   CH.sub.3                                                                            O  Br                                               H      H     H  H   CH.sub.3 O                                                                          O  Br                                               H      H     H  H   Cl    O  Br                                               H      H     H  H   H     O  Br                                               H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         Br                                               H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Br                                               H      H     H  H   CH.sub.3                                                                            O                                                                                 ##STR198##                                      H      H     H  H   CH.sub.3 O                                                                          O                                                                                 ##STR199##                                      H      H     H  H   Cl    O                                                                                 ##STR200##                                      H      H     H  H   H     O                                                                                 ##STR201##                                      H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                          ##STR202##                                      H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                          ##STR203##                                      H      H     H  H   CH.sub.3                                                                            O                                                                                 ##STR204##                                      H      H     H  H   CH.sub.3 O                                                                          O                                                                                 ##STR205##                                      H      H     H  H   Cl    O                                                                                 ##STR206##                                      H      H     H  H   H     O                                                                                 ##STR207##                                      H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                          ##STR208##                                      H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                          ##STR209##                                      H      H     H  H   CH.sub.3                                                                            O  +NMe.sub.3                                       H      H     H  H   CH.sub.3 O                                                                          O  +NMe.sub.3                                       H      H     H  H   Cl    O  +NMe.sub.3                                       H      H     H  H   H     O  +NMe.sub.3                                       H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         +NMe.sub.3                                       H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         +NMe.sub.3                                       H      H     H  H   CH.sub.3                                                                            O  NH.sub.2                                         H      H     H  H   CH.sub.3 O                                                                          O  NH.sub.2                                         H      H     H  H   Cl    O  NH.sub.2                                         H      H     H  H   H     O  NH.sub.2                                         H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         NH.sub.2                                         H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         NH.sub.2                                         H      H     H  H   CH.sub.3                                                                            O  NHCOCH.sub.3                                     H      H     H  H   CH.sub.3 O                                                                          O  NHCOCH.sub. 3                                    H      H     H  H   Cl    O  NHCOCH.sub.3                                     H      H     H  H   H     O  NHCOCH.sub.3                                     H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         NHCOCH.sub.3                                     H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         NHCOCH.sub.3                                     H      H     H  H   CH.sub.3                                                                            O                                                                                 ##STR210##                                      H      H     H  H   CH.sub.3 O                                                                          O                                                                                 ##STR211##                                      H      H     H  H   Cl    O                                                                                 ##STR212##                                      H      H     H  H   H     O                                                                                 ##STR213##                                      H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                          ##STR214##                                      H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                          ##STR215##                                      H      H     H  H   CH.sub.3                                                                            O  NHCH.sub.3                                       H      H     H  H   CH.sub.3 O                                                                          O  NHCH.sub.3                                       H      H     H  H   Cl    O  NHCH.sub.3                                       H      H     H  H   H     O  NHCH.sub.3                                       H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         NHCH.sub.3                                       H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         NHCH.sub.3                                       H      H     H  H   CH.sub.3                                                                            O  NCH.sub.3 CONHCH.sub.3                           H      H     H  H   CH.sub.3 O                                                                          O  NCH.sub.3 CONHCH.sub.3                           H      H     H  H   Cl    O  NCH.sub.3 CONHCH.sub.3                           H      H     H  H   H     O  NCH.sub.3 CONHCH.sub.3                           H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         NCH.sub.3 CONHCH.sub.3                           H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         NCH.sub.3 CONHCH.sub.3                           H      H     H  H   CH.sub.3                                                                            O  N(C.sub.2 H.sub.5)CO.sub.2 CH.sub.3              H      H     H  H   CH.sub.3 O                                                                          O  N(C.sub.2 H.sub.5)CO.sub.2 CH.sub.3              H      H     H  H   Cl    O  N(C.sub.2 H.sub.5)CO.sub.2 CH.sub.3              H      H     H  H   H     O  N(C.sub.2 H.sub.5)CO.sub.2 CH.sub.3              H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         N(C.sub.2 H.sub.5)CO.sub.2 CH.sub.3              H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         N(C.sub.2 H.sub.5)CO.sub.2 CH.sub.3              H      H     H  H   CH.sub.3                                                                            O  NHCO.sub.2 Et                                    H      H     H  H   CH.sub.3 O                                                                          O  NHCO.sub.2 Et                                    H      H     H  H   Cl    O  NHCO.sub.2 Et                                    H      H     H  H   H     O  NHCO.sub.2 Et                                    H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         NHCO.sub.2 Et                                    H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         NHCO.sub.2 Et                                    H      H     H  H   CH.sub.3                                                                            O  Cl                                               H      H     H  H   CH.sub.3 O                                                                          O  Cl                                               H      H     H  H   Cl    O  Cl                                               H      H     H  H   H     O  Cl                                               H      H     H  H   CH.sub.3                                                                            CH.sub.2                                                                         Cl                                               H      H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               H      Cl    H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               H      CH.sub.3                                                                            H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               H      CH(CH.sub.3).sub.2                                                                  H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               H      H     CH.sub.3                                                                         H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5-F    H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5Cl    H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5Br    H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5-NO.sub.2                                                                           H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5-CF.sub.3                                                                           H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5-CH.sub.3                                                                           H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5-CH(CH.sub.3).sub.2                                                                 H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5-OCH.sub.3                                                                          H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               5-OCH(CH.sub.3).sub.2                                                                H     H  H   CH.sub.3 O                                                                          CH.sub.2                                                                         Cl                                               H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                         NCH.sub.3 (OCH.sub.3)                            H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                         NHn-C.sub.4 H.sub.9                              H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR216##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR217##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR218##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR219##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR220##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR221##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR222##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR223##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR224##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR225##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR226##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR227##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR228##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR229##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR230##                                      H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                          ##STR231##                                      H      H     H  H   OCH.sub.2 CH.sub.3                                                                  CH.sub.2                                                                         Cl                                               H      H     H  H   OCH.sub.2 CH.sub.3                                                                  O  Cl                                               H      H     H  H   OCH.sub.2 CH.sub.3                                                                  CH.sub.2                                                                         Cl                                               H      H     H  H   OCH.sub.2 CH.sub.3                                                                  O  Cl                                               H      H     H  CH.sub.3                                                                          CH.sub.3                                                                            O  Cl                                               H      H     H  CH.sub.3                                                                          CH.sub.3                                                                            CH.sub.2                                                                         Cl                                               H      H     H  CH.sub.3                                                                          OCH.sub.3                                                                           O  Cl                                               H      H     H  CH.sub.3                                                                          OCH.sub.3                                                                           CH.sub. 2                                                                        Cl                                               H      H     H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH.sub.2                                                                         Cl                                               H      H     H  CH.sub.3                                                                          CH.sub.3                                                                            O  F                                                H      H     H  CH.sub.3                                                                          OCH.sub.3                                                                           CH.sub.2                                                                         F                                                H      H     H  CH.sub.3                                                                          OCH.sub.3                                                                           O  F                                                H      F     H  H   OCH.sub.3                                                                           O  F                                                H      F     H  H   CH.sub.3                                                                            O  F                                                H      F     H  H   OCH.sub.3                                                                           CH.sub.2                                                                         F                                                H      H     H  H   OCH.sub.3                                                                           O  F                                                H      H     H  H   CH.sub.3                                                                            O  F                                                H      H     H  H   OCH.sub.3                                                                           CH.sub.2                                                                         F                                                __________________________________________________________________________

                  TABLE IV                                                        ______________________________________                                         ##STR232##                                                                   R     R.sub.1                                                                              R.sub.2                                                                              Y'       R.sub.8                                                                              L                                         ______________________________________                                        H     H      H      CH.sub.3 H      Cl                                        H     H      H      OCH.sub.3                                                                              H      Cl                                        H     Cl     H      CH.sub.3 H      Cl                                        H     Cl     H      OCH.sub.3                                                                              H      Cl                                        H     H      H      OCH.sub.2 CH.sub.3                                                                     H      Cl                                        H     Cl     H      OCH.sub.2 CH.sub.3                                                                     H      Cl                                        H     H      H      CH.sub.3 H                                                                                     ##STR233##                               H     H      H      OCH.sub.3                                                                              H                                                                                     ##STR234##                               H     H      H      OCH.sub.2 CH.sub.3                                                                     H                                                                                     ##STR235##                               H     H      H      CH.sub.3 H      N.sup.⊕ (CH.sub.3).sub.3              H     H      H      OCH.sub. 3                                                                             H      N.sup.⊕ (CH.sub.3).sub.3              H     H      H      OCH.sub.2 CH.sub.3                                                                     H      N.sup.⊕ (CH.sub.3).sub.3              H     H      H      CH.sub.3 H                                                                                     ##STR236##                               H     H      H      OCH.sub.3                                                                              H                                                                                     ##STR237##                               H     H      H      OCH.sub.2 CH.sub.3                                                                     H                                                                                     ##STR238##                               H     H      H      OCH.sub.3                                                                              H                                                                                     ##STR239##                               H     H      H      OCH.sub.2 CH.sub.3                                                                     H                                                                                     ##STR240##                               5-Cl  H      Cl     CH.sub.3 H      Cl                                        5-Cl  H      Cl     OCH.sub.3                                                                              H      Cl                                        5-Cl  H      Cl     OCH.sub.2 CH.sub.3                                                                     H      Cl                                        H     H      H      CH.sub.3 CH.sub.3                                                                             Cl                                        H     H      H      OCH.sub.3                                                                              CH.sub.3                                                                             Cl                                        H     H      H      CH.sub.3 OCH.sub.3                                                                            Cl                                        H     H      H      OCH.sub.3                                                                              OCH.sub.3                                                                            Cl                                        H     H      H      OCH.sub.3                                                                              H      F                                         H     H      H      CH.sub.3 H      F                                         H     F      H      OCH.sub.3                                                                              H      F                                         H     F      H      CH.sub.3 H      F                                         H     H      H      OCH.sub.3                                                                              CH.sub.3                                                                             F                                         ______________________________________                                    

                  TABLE V                                                         ______________________________________                                         ##STR241##                                                                   L              R.sub.1  R.sub.2   R                                           ______________________________________                                        Cl             H        H         H                                           Cl             Cl       H         H                                           Br             H        H         H                                           Br             Cl       H         H                                           Cl             H        CH.sub.3  H                                            ##STR242##    H        H         H                                           F              H        H         H                                           F              F        H         H                                           N(CH.sub.3)    H        H         H                                            ##STR243##    H        H         H                                           Cl             H        H         5-NO.sub.2                                  Cl             Cl       H         5-NO.sub.2                                  Br             H        H         5-NO.sub.2                                  Br             Cl       H         5-NO.sub.2                                  Cl             H        CH.sub.3  5-NO.sub.2                                   ##STR244##    H        H         5-NO.sub.2                                  N(CH.sub.3).sub.2                                                                            H        H         5-NO.sub.2                                   ##STR245##                                                                   Cl             H        H         5-Cl                                        Cl             Cl       H         5-Cl                                        Br             H        H         5-Cl                                        Br             Cl       H         5-Cl                                        Cl             H        CH.sub.3  5-Cl                                         ##STR246##    H        H         5-Cl                                        N(CH.sub.3).sub.2                                                                            H        H         5-Cl                                         ##STR247##    H        H         5-Cl                                        ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                         ##STR248##                                                                   L         R         R.sub.1 R.sub.2                                                                             Z    m.p.(°C.)                       ______________________________________                                        Cl        H         H       H     CH                                          Cl        H         H       Cl    CH                                          Br        H         H       H     N                                            ##STR249##                                                                             H         H       H     CH                                          Cl        5-NO.sub.2                                                                              H       H     CH                                          Cl        5-Cl      H       H     CH                                          Cl        5-Cl      H       Cl    N                                            ##STR250##                                                                             H         H       H     CH                                           ##STR251##                                                                             H         H       H     N                                           N(CH.sub.3).sub.2                                                                       H         H       H     CH                                          Cl        5-CF.sub.3                                                                              H       H     CH                                          Cl        5-OCH.sub.3                                                                             H       H     N                                           Cl        5-CH.sub.3                                                                              H       H     CH                                           ##STR252##                                                                             H         H       H     CH                                          Cl        H         H       C.sub.2 H.sub.5                                                                     N                                           Cl        H         CH.sub.3                                                                              Cl    CH                                          F         H         H       H     CH                                          F         H         F       H     N                                           ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). Morespecifically, they will contain these ingredients in the followingapproximate proportions:

                  TABLE VII                                                       ______________________________________                                                    Active*                                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90     0-74      1-10                                        Oil Suspensions,                                                                            3-50      40-95     0-15                                        Emulsions, Solu-                                                              tions (including                                                              Emulsifiable                                                                  Concentrates                                                                  Aqueous Suspensions                                                                         10-50     40-84     1-20                                        Dusts         1-25      70-99     0-5                                         Granules and  0.1-95    5-99.9    0-15                                        Pellets                                                                       High Strength 90-99     0-10      0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a surfactant or a diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, New Jersey. The more absorptive diluents are preferred forwettable powders and the denser ones for dusts. Typical liquid diluentsand solvents are described in Marsden, "Solvents Guide", 2nd Ed.,Interscience, New York, 1950. Solubility under 0.1% is preferred forsuspension concentrates; solution concentrates are preferably stableagainst phase separation at 0° C. "McCutcheon's Detergents andEmulsifiers Annual," MC Publishing Corp., Ridgewood, N.J., as well asSisely and Wood, "Encyclopedia of Surface Active Agents," ChemicalPublishing Co., Inc., New York 1964, list surfactants and recommendeduses. All formulations can contain minor amounts of additives to reducefoam, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 1, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182.

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 5,line 66 through Col. 5, line 17 and Examples 1-4.

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 21

Wettable Powder

2-(chloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl)benzenesulfonamide--80%

sodium alkylnaphthalenesulfonate--2%

sodium ligninsulfonate--2%

synthetic amorphous silica--3%

kaolinite--13%

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns and then reblended.

EXAMPLE 22

Wettable Powder

2-(dichloromethyl)-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide--50%

sodium alkylnaphthalenesulfonate--2%

low viscosity methyl cellulose--2%

diatomaceous earth--46%

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles of active essentially all below 10 microns indiameter. The product is reblended before packaging.

EXAMPLE 23

Granule

wettable powder of Example 22--5%

attapulgite granules--95%

(U.S.S. 20-40 mesh; 0.84-0.42 mm)

A slurry of wettable powder containing≈25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 24

Extruded Pellet

2-(chloromethyl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide--25%

anhydrous sodium sulfate--10%

crude calcium ligninsulfonate--5%

sodium alkylnaphthalenesulfonate--1%

calcium/magnesium bentonite--59%

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 25

Oil Suspension

2-(1-chloroethyl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide--25%

polyoxyethylene sorbitol hexaoleate--5%

highly aliphatic hydrocarbon oil--70%

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 26

Wettable Powder

2-(1-chloroethyl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide--20%

sodium alkylnaphthalenesulfonate--4%

sodium ligninsulfonate--4%

low viscosity methyl cellulose--3%

attapulgite--69%

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 27

Aqueous Suspension

2-(dichloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide--40%

polyacrylic acid thickener--0.3%

dodecylphenol polyethylene glycol ether--0.5%

disodium phosphate--1%

monosodium phosphate--0.5 %

polyvinyl alcohol--1.0%

Water--56.7%

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 28

Solution

2-(chloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide,sodium salt--5%

Water--95%

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 29

Low Strength Granule

2-(chloromethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide--0.1%

attapulgite granules --99.9%

(U.S.S. 20-40 mesh)

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 30

Granule

2-(dichloromethyl)-N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide--80%

wetting agent--1%

crude ligninsulfonate salt (containing 5-20% of the natural sugars)--10%

attapulgite clay--9%

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water constant is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 31

High Strength Concentrate

2-(dichloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide--99%

silica aerogel--0.5%

synthetic amorphous silica--0.5%

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 32

Wettable Powder

2-(chloromethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide--90%

dioctyl sodium sulfosuccinate--0.1%

synthetic fine silica--9.9%

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 33

Wettable Powder

2-(chloromethyl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide--40%

sodium ligninsulfonate--20%

montmorillonite clay--40%

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

Utility

The compounds of the present invention are active herbicides. They haveutility for broadspectrum pre- and/or post-emergence weed control inareas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,oil well sites, drive-in theaters, around billboards, highway andrailroad structures. By properly selecting rate and time of application,compounds of this invention may be used to modify plant growthbeneficially, and also selectively control weeds in crops such as wheatand barley.

The precise amount of the compound of Formula I to be used in any givensituation will vary according to the particular end result desired, theamount of foliage present, the weeds to be controlled, the soil type,the formulation and mode of application, weather conditions, etc. Sinceso many variables play a role, it is not possible to state a rate ofapplication suitable for all situations. Broadly speaking, the compoundsof this invention are used at levels of about 0.001 to 20 kg/ha with apreferred range of 0.01 to 10 kg/ha. In general, the higher rates ofapplication from within this range will be selected for adverseconditions or where extended persistence in soil is desired.

The compounds of Formula I may be combined with other herbicides and areparticularly useful in combination with3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron); the triazines such as2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (atrazine); theuracils such as 5-bromo-3-sec-butyl-6-methyluracil (bromacil);N-(phosponomethyl)glycine (glyphosate);3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione(hexazinone); N,N-dimethyl-2,2-diphenylacetamide (diphenamide);2,4-dichlorophenoxyacetic acid (2,4-d) (and closely related compounds);4-chloro-2-butynyl-3-chlorophenylcarbamate (barban);S-(2,3-dichloroallyl)diisopropylthiocarbamate (diallate);S-(2,3,3-trichloroallyl)diisopropylthiocarbamate (triallate);1,2-dimethyl-3,5-diphenyl-1H-pyrazolium methyl sulfate (difenzoquatmethyl sulfate); methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate(diclofop methyl);4-amino-6-tertbutyl-3-(methylthio)-1,2,4-triazin-5(4H)one (metribuzin);3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron);3-isopropyl-1H-2,1,3-benzothiodiazin-4(3H)-one-2,2-dioxide (bentazon);α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine (trifluralin);1,1'-dimethyl-4,4'-dipyridinium ion (paraquat); monosodiummethanearsonate (MSMA); 2-chloro-2',6'-diethyl(methoxymethyl)acetanilide(alachlor); and 1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea(fluometuron), and5-[2-chloro-4-(trifluoromethyl)phenoxy]-z-nitrobenzoic acid, methylester (acifluorfen, methyl).

Test Procedure A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory(Ipomoea spp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice,wheat and nutsedge tubers (Cyperus rotundus) were planted in a growthmedium and treated pre-emergence with a nonphytotoxic solvent solutionof the compounds of Table IV. At the same time, cotton having fiveleaves (including cotyledonary ones), bush beans with the thirdtrifoliate leaf expanding, crabgrass with two leaves, barnyardgrass withtwo leaves, wild oats with two leaves, cassia with three leaves(including cotyledonary ones), morningglory with four leaves (includingthe cotyledonary ones), cocklebur with four leaves (including thecotyledonary ones), sorghum with four leaves, corn with four leaves,soybean with two cotyledondary leaves, rice with three leaves, wheatwith one leaf, and nutsedge with three-five leaves were sprayed with anonphytotoxic solvent solution of the compounds of Table A. Othercontainers of the above mentioned weeds and crops were treated pre- orpost-emergence with the same nonphytotoxic solvent so as to provide asolvent control. A set of untreated control plants was also included forcomparison. Pre-emergence and post-emergence treated plants and controlswere maintained in a greenhouse for sixteen days, then all treatedplants were compared with their respective controls and rated visuallyfor response to treatment.

The ratings are based on a numberical scale extending from 0=no injury,to 10=complete kill. The accompanying descriptive symbols have thefollowing meanings:

G=growth retardation

C=chlorosis/necrosis

E=emergence inhibition

H=formative effects

D=defoliation

6Y=abscised buds or flowers

U=unusual pigmentation.

    TABLE A              BARN-       kg/ BUSH  MORNING- COCK- CAS- NUT- CRAB- YARD- WILD       SOY-  SOR- ha BEAN COTTON GLORY LEBUR SIA SEDGE GRASS GRASS OATS WHEAT     CORN BEAN RICE GHUM       POST-EMERGENCE      ##STR253##      0.4 9D,8G,6Y 5U,9D,9G 10C 9C 9C 2C,9G 2C,8G 10C 9C 2C,9G 3U,9C 5C,9G     9C      ##STR254##       0.4 9C 9C 10C 9C 9C 9C 2C 9C 3C,8H 9C 9C 9C 6C,9G 10C      ##STR255##      0.4 7C 3C 1C 10C 1C 0 0 0 0 0 2C,3H 7C 0 2C      ##STR256##      0.1 5C,9G,6Y 3C,3H,9G 1C,2H 2C,9G 3C,5H 2C,7G 1C,3G 3C,9H 1C 1C 2C,9H     9C 1C,8G 1C,9H      ##STR257##      0.1 10G,5H 0 10G,7C 10G 6G,3C 3G 4G 0 0 0 7G,5H 10G,9C 8G,3C 10C      ##STR258##      0.4 8C 8C 10C 9C 8C 3G 3C 7C 3G 0 10C 8C 7C 7C      ##STR259##      0.4 7C,9G 9C 9C 9C 2C,5G 7C,9G 1C,4G 2C 0 0 5U,9C 9C 0 1C,7H      ##STR260##      0.1 3C,8G,6Y 9C,5G 6C,9G 4C,9G 2C,3G 4G 3G 9H 1C 0 3C,9H 2C,9G 9C 3C,9G      ##STR261##      0.1 8D,9G,6Y 5C,9G 6C,9G 4C,9G 2C,7G 5G 1C 2C,9H 2C 1C 3C,9H 2C,9G     3C,9G 2C,9G PRE-EMERGENCE      ##STR262##      0.4 9G 9G 9G 9G 8G 5C,9H 3C,9G 9G 9G 9H 10E 5C,9H      ##STR263##      0.4 9H 9H 4C,9G 10H 3C,7G 3C,9H 2C,9G 2C,9G 9H 9H 10E 10E      ##STR264##      0.4 3G 6G,5C 5G 0 0 3G 0 0 3C 2C 0 4G      ##STR265##      0.1 8G 8H 8G 10E 5G 2C,8H 7G 4G 8H 5H 10E 1C,9G      ##STR266##      0.1 9C 6G 5G 8G 4G 5C 5G 5G 5G,2C 6G,3C 7G,4C 5G,3H      ##STR267##      0.4 8C 8C 5G 3G 3C 8C 6C 6G 9C 9C 10C 9C      ##STR268##      0.4 9G 9H 9G 9G 2C,7G 2C,9H 2C,6G 3G 9H 9H 9H 1C,9H      ##STR269##      0.1 9G 2C 3C 3G 1C 1C 0 0 2C,6G 2C,2H 2C,8G 3C,8H      ##STR270##      0.1 2C,9G 2C,5H 2C,3H 4G 1C 1C,3G 0 0 3C,8G 2C,7H 3C,7G 3C,9G

Test B

Two plastic bulb pans were filled with fertilized and limed Fallsingtonsilt loam soil. One pan was planted with corn, sorghum, Kentuckybluegrass and several grassy weeds. The other pan was planted withcotton, soybeans, purple nutsedge (Cyperus rotundus), and severalbroadleaf weeds. The following grassy and broadleaf weeds were planted:crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense),dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii),cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur(Xanthium pensylvanicum), pigweed (Amaranthus retroflexus), morningglory(Ipomoea hederacea), cassia (Cassia tora), teaweed (Sida spinosa),velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A12.5 cm diameter plastic pot was also filled with prepared soil andplanted with rice and wheat. Another 12.5 cm pot was planted withsugarbeets. The above four containers were treated pre-emergence withseveral test compounds within the scope of the invention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table B.

                                      TABLE B                                     __________________________________________________________________________    PRE-EMERGENCE ON FALLSINGTON SILT LOAM                                        __________________________________________________________________________             ##STR271##                                                           Rate kg/ha                                                                            0.015      0.03       0.06       0.25                                 __________________________________________________________________________    Crabgrass                                                                             0          0          6G         8G,6C                                Barnyardgrass                                                                         0          0          9G,9C      10C                                  Sorghum 5G         7G,3H      10C        10E                                  Wild Oats                                                                             0          0          7G,5C      10C                                  Johnsongrass                                                                          0          4G,3H      9G,9C      10C                                  Dallisgrass                                                                           0          2G         8G,5C      10C                                  Giant foxtail                                                                         0          4G         10C        10C                                  Ky. bluegrass                                                                         5G         6G,3C      10C        10C                                  Cheatgrass                                                                            4G         4G         10E        10E                                  Sugarbeets                                                                            0          5G         10C        10C                                  Corn    0          0          10C        10C                                  Mustard 9G,8C      9G,8C      10C        10C                                  Cocklebur                                                                             6G,3H      6G,3H      8G,5H      8G,8C                                Pigweed --         --         --         --                                   Nutsedge                                                                              0          0          9G         10E                                  Cotton  0          2G         9G         10C                                  Morningglory                                                                          2G         5G         10C        10C                                  Cassia  0          5G         10C        10C                                  Teaweed 0          0          10C        10C                                  Velvetleaf                                                                            0          0          10C        10C                                  Jimsonweed                                                                            0          0          6G         10C                                  Soybean 0          0          9G,9C      9G,8C                                Rice    5G         6G         10E        10E                                  Wheat   2G         4G         8G,8C      10C                                  __________________________________________________________________________     ##STR272##                                                                                                  ##STR273##                                     Rate kg/ha                                                                            0.125      0.5        0.03       0.25                                 __________________________________________________________________________    Crabgrass                                                                             0          3G         0          0                                    Barnyardgrass                                                                         5G,3C      7G,3C      0          3G                                   Sorghum 8G,5H      10C        4G         7G,5H                                Wild Oats                                                                             0          0          0          0                                    Johnsongrass                                                                          5G         7G         0          3G                                   Dallisgrass                                                                           0          3G         0          0                                    Giant foxtail                                                                         5G         10E        0          0                                    Ky. bluegrass                                                                         6G,3C      8G,8C      0          0                                    Cheatgrass                                                                            3G         7G,5C      0          5G                                   Sugarbeets                                                                            7G,5H      8G,8C      0          2G                                   Corn    8G,5H      9G,9C      0          2C                                   Mustard 10C        10C        0          8G,3C                                Cocklebur                                                                             7G         9G,8C      0          2G                                   Pigweed --         --         5G         5G                                   Nutsedge                                                                              3G         6G         0          7G                                   Cotton  8G         9G,8C      0          0                                    Morningglory                                                                          8G         9G,8C      0          0                                    Cassia  8G,8C      8G,8C      3G         4G                                   Teaweed 10C        10C        0          2G                                   Velvetleaf                                                                            8G,9C      10C        0          6G                                   Jimsonweed                                                                            0          3G         0          0                                    Soybean 8G,5H      9G,5H      0          0                                    Rice    0          6G,4C      4G         5G                                   Wheat   0          0          0          3G                                   __________________________________________________________________________                                   ##STR274##                                                           Rate kg/ha                                                                            0.03        0.125                               __________________________________________________________________________                          Crabgrass                                                                             0          0                                                          Barnyardgrass                                                                         0          4G                                                         Sorghum 4G         7G,3H                                                      Wild Oats                                                                             0          0                                                          Johnsongrass                                                                          0          7G,3H                                                      Dallisgrass                                                                           6G         10E                                                        Giant foxtail                                                                         0          0                                                          Ky. bluegrass                                                                         0          5G                                                         Cheatgrass                                                                            0          0                                                          Sugarbeets                                                                            0          0                                                          Corn    0          3G                                                         Mustard 4G         10C                                                        Cocklebur                                                                             0          0                                                          Pigweed 0          5G                                                         Nutsedge                                                                              0          0                                                          Cotton  0          0                                                          Morningglory                                                                          0          0                                                          Cassia  0          3G                                                         Teaweed 0          2G                                                         Velvetleaf                                                                            0          7G,3H                                                      Jimsonweed                                                                            0          0                                                          Soybean 0          6G,3H                                                      Rice    0          6G,3H                                                      Wheat   0          0                                    __________________________________________________________________________

Test C

Twenty-five cm diameter plastic pots filled with Fallsington silt loamwere planted with soybeans, cotton, alfalfa, corn, rice, wheat, sorghum,velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), Cassia(Cassia tora), morningglory (Ipomoea hederacea), jimsonweed (Daturastramonium), cocklebur (Xanthium pennsylvanicum), crabgrass (Digitariaspp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloacrusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua).Approximately two weeks after planting, the young plants and the soilaround them were sprayed overall with the test chemicals dissolved in anon-phytotoxic solvent. Two weeks after treatment, all species werecompared to untreated controls and visually rated for response totreatment. The rating system was as described previously for Test A. Thedata are presented in Table C.

                  TABLE C                                                         ______________________________________                                                  ##STR275##                                                          Rate kg/ha 0.06           0.25                                                ______________________________________                                        Soybeans   10G, 6C        10G, 8C                                             Velvetleaf 10G, 6C        10G, 8C                                             Sesbania   9C             9C                                                  Cassia     10G, 5C        10G, 7C                                             Cotton     9C             9C                                                  Morningglory                                                                             10G, 7C        10G, 8C                                             Alfalfa                   9C                                                  Jimsonweed                                                                    Cocklebur  10G, 9C        10G, 8C                                             Corn       9G, 3C         9C                                                  Crabgrass  0              3G, 1C                                              Rice       6G, 1C         8G, 2C                                              Nutsedge   6G             9G                                                  Barnyardgrass                                                                            6G, 3C         8G, 3C                                              Wheat      3G, 2C         7G, 2C                                              Giant Foxtail                                                                            4G             9G                                                  Wild Oats  5G             7G, 2C                                              Sorghum    9G, 3C         10 , 7C                                             ______________________________________                                                  ##STR276##                                                          Rate kg/ha 0.03           0.125                                               ______________________________________                                        Soybeans   10G, 6C        10G, 7C                                             Velvetleaf 6G             7G, 3C                                              Sesbania   10G, 3C        10G, 9C                                             Cassia     3G, 1C         8G, 1C                                              Cotton     3G, 1C         4G, 2C                                              Morningglory                                                                             5G             5G, 1C                                              Alfalfa    5G, 2C         7G, 3C                                              Jimsonweed                                                                    Cocklebur  4G             3G, 1C                                              Corn       5G, 5H         9G, 5C                                              Crabgrass  2G             3G, 1C                                              Rice       5G             8G, 3C                                              Nutsedge   4G             7G, 2C                                              Barnyardgrass                                                                            5G, 1C         8G, 2C                                              Wheat      0              0                                                   Giant Foxtail                                                                            6G, 1C         8G, 2C                                              Wild Oats  0              0                                                   Sorghum    5G, 1C         7G, 2C                                              ______________________________________                                    

Test D

Two ten-inch in diameter plastic pans lined with polyethylene linerswere filled with prepared Fallsington silt loam soil. One pan wasplanted with seeds of wheat (Triticum aestivum), barley (Hordeumvulgare), wild oats (Avena fatua), downy brome (Bromus tectorum),cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides),annual bluegrass (Poa annua), green foxtail (Setaria viridis),quackgrass (Agropyron repens), Italian ryegrass (Lolium multiflorum) andripgut brome (Bromus rigidus). The other pan was planted with seeds ofRussian thistle (Salsola kali), tansy mustard (Descuraina pinnata),smartweed (Polygonum pennsylvanicum), tumble mustard (Sisymbriumaltissium) kochia (Kochia scoparia), shepherd's purse (Capsellabursa-pastoris), Matricaria inodora, black nightshade (Solanum nigrum),yellow rocket (Barbarea vulgaris), wild mustard (Brassica kaber) andwild buckwheat (Polygonum convolvulus). The above two pans were treatedpre-emergence. At the same time two pans in which the above plantspecies were growing were treated post-emergence. Plant height at thetime of treatment ranged from 1-15 cm depending on plant species.

The compounds applied were diluted with a non-phytotoxic solvent andsprayed over-the-top of the pans. An untreated control and a solventalong control were included for comparison. All treatments weremaintained in the greenhouse for 20 days at which time the treatmentswere compared to the controls and the effects visually rated. Therecorded data are presented in Table D.

Several of the compounds tested by this procedure have utility for thepre- and/or post-emergence control of weeds in cereal crops such aswheat and barley.

                  TABLE D                                                         ______________________________________                                                  ##STR277##                                                                     Post-emergence Pre-emergence                                       Rate kg/ha 0.015          0.015                                               ______________________________________                                        wheat      0              0                                                   barley     0              0                                                   wild oats  0              0                                                   downy brome                                                                              0              0                                                   cheatgrass 0              0                                                   blackgrass 2C             2G                                                  annual bluegrass                                                                         0              1G                                                  green foxtail                                                                            0              0                                                   quackgrass 0              0                                                   Italian ryegrass                                                                         0              0                                                   ripgut brome                                                                             0              0                                                   Russian thistle                                                                          10C            0                                                   tansy mustard                                                                            10C            7C, 8G                                              smartweed  9C             --                                                  jimhill mustard                                                                          10C            9C, 8G                                              Kochia     7C, 8G         5C, 5G                                              shepherd's purse                                                                         10C            9C, 8G                                              false chamomile                                                                          10C            5C, 8G                                              black nightshade                                                                         --             --                                                  yellow rocket                                                                            10C            10C                                                 wild mustard                                                                             10C            7C, 7G                                              wild buckwheat                                                                           6C, 5G         1C, 1G                                              ______________________________________                                                   Post-emergence Pre-emergence                                       Rate kg/ha 0.06           0.06                                                ______________________________________                                        wheat      0              0                                                   barley     0              0                                                   wild oats  0              1G                                                  downy brome                                                                              1G             0                                                   cheatgrass 0              1G                                                  blackgrass 7C             3G                                                  annual bluegrass                                                                         2C, 2G         3C, 7G                                              green foxtail                                                                            10C            3G                                                  quackgrass 0              3G                                                  Italian ryegrass                                                                         2G             5G                                                  ripgut brome                                                                             0              0                                                   Russian thistle                                                                          10C            3C, 3G                                              tansy mustard                                                                            10C            8C, 8G                                              smartweed  10C            --                                                  jimhill mustard                                                                          10C            9C 9G                                               Kochia     9C             7C, 8G                                              shepherd's purse                                                                         10C            10C                                                 false chamomile                                                                          10C            7C, 8G                                              black nightshade                                                                         --             --                                                  yellow rocket                                                                            10C            10C                                                 wild mustard                                                                             10C            9C, 8G                                              wild buckwheat                                                                           8C, 7G         2C, 3G                                              ______________________________________                                                   Post-emergence Pre-emergence                                       Rate kg/ha 0.125          0.125                                               ______________________________________                                        wheat      0              0                                                   barley     0              0                                                   wild oats  0              0                                                   downy brome                                                                              0              2G                                                  cheatgrass 0              3G                                                  blackgrass --             4C, 8G                                              annual bluegrass                                                                         2G             6G                                                  green foxtail                                                                            4C, 4G         2C, 6G                                              quackgrass 0              3G                                                  Italian ryegrass                                                                         2C, 4G         2G                                                  ripgut brome                                                                             0              0                                                   Russian thistle                                                                          10C            4C, 5G                                              tansy mustard                                                                            10C            9C, 9G                                              smartweed  --             --                                                  jimhill mustard                                                                          10C            9C, 9G                                              Kochia     10C            5G                                                  shepherd's purse                                                                         10C            8C, 9G                                              false chamomile                                                                          10C            9C, 9G                                              black nightshade                                                                         --             5G                                                  yellow rocket                                                                            10C            9C, 9G                                              wild mustard                                                                             10C            7C, 8G                                              wild buckwheat                                                                           10C            2C, 2G                                              ______________________________________                                                   Post-emergence Pre-emergence                                       Rate kg/ha 0.5            0.5                                                 ______________________________________                                        wheat      0              0                                                   barley     0              1G                                                  wild oats  0              0                                                   downy brome                                                                              2G             1G                                                  cheatgrass 2G             3C, 4G                                              blackgrass --             2C, 6G                                              annual bluegrass                                                                         6C, 5G         5C, 7G                                              green foxtail                                                                            10C            4C, 7G                                              quackgrass 2G             7C, 7G                                              Italian ryegrass                                                                         4C, 6G         5G                                                  ripgut brome                                                                             0              2G                                                  Russian thistle                                                                          10C            5C, 5G                                              tansy mustard                                                                            10C            9C, 9G                                              smartweed  --             --                                                  jimhill mustard                                                                          10C            9C, 9G                                              Kochia     10C            6G                                                  shepherd's purse                                                                         10C            9C, 9G                                              false chamomile                                                                          10C            9C, 9G                                              black nightshade                                                                         --             4C, 6G                                              yellow rocket                                                                            10C            9C, 9G                                              wild mustard                                                                             10C            9C, 9G                                              wild buckwheat                                                                           10C            5C, 6G                                              ______________________________________                                    

Test E

Test samples were formulated and applied directly to the water ofpaddies three days after transplanting of Japonica rice. The paddieswere maintained in a greenhouse, and plant response ratings were takenone and three weeks after application.

    ______________________________________                                         ##STR278##                                                                                            Barnyard-*                                                                            Water*                                       Treat- Rice     Rice     grass   Chestnut                                                                             Scirpus*                              ment   1 Week   3 Weeks  3 Weeks 3 Weeks                                                                              3 Weeks                               ______________________________________                                         5 g/ha                                                                              0        0        5G      8G     0                                     20 g/ha                                                                              0        5G       8G      9G     5G                                    ______________________________________                                         *Echinochloa sp., Eleocharis sp., and Scirpus sp., respectively.         

Test F

Purple nutsedge (Cyperus rotundus) tubers were planted about 2 cm deepin Fallsington slit loam soil contained in 10 cm diameter plastic pots.Five tubers were planted in each pot. Compounds of this invention weredissolved in a non-phytotoxic diluent and sprayed at 560 l/ha in fourmethods of application: soil surface, tuber/soil, soil incorporated andpost-emergence. The soil surface spray consisted of spraying thecompound on the surface of the firmed covering soil. The tuber/soilspray consisted of spraying the compound on exposed tubers andsubtending soil before adding the untreated covering soil. Soilincorporated treatment consisted in mixing the compound with thecovering soil before using it to cover the tubers. The post-emergencetreatment was sprayed on nutsedge foliage and the surrounding soilsurface when nutsedge had emerged and grown to a height of about 12 cm.Pots receiving the post-emergence treatments were placed directly in thegreenhouse. Pots receiving the other treatments were misted with about0.3 cm water before being transferred to the greenhouse. Responseratings assessed after four weeks are recorded in Table F based on thesame rating system as described in procedure A.

    ______________________________________                                        TEST F                                                                        NUTSEDGE                                                                       ##STR279##                                                                   Response Rating (after 4 weeks)                                               Rate    Preemerg.  Tuber     Soil                                             kg/ha   Soil Surface                                                                             Spray     Incorp.                                                                             Postemerg.                                 ______________________________________                                        0.01    3G         6G        7G    0                                          0.03    7G         7G        8G    0                                          0.125   9G         9G        9G    4C, 7G                                     ______________________________________                                    

What is claimed is:
 1. A compound selected from ##STR280## wherein L isCl, F, Br, NR₃ R₄, N⁺ R₃ R₄ R₄ ', N(R₄)C(O)R₅, N(R₄)C(O)NHR₆ orN(R₄)C(O)OR₇ ;R is H, F, Cl, Br, NO₂, CF₃, C₁ -C₃ alkyl or C₁ -C₃alkoxy; R₁ is H, F, Cl or C₁ -C₄ alkyl; R₂ is H or CH₃ ; R₃ is H, C₁ -C₄alkyl or OCH₃ ; R₄ is H or C₁ -C₄ alkyl; R₃ and R₄ can be taken togetherto form --(CH₂)₄ --, --(CH₂)₅ -- or --(CH₂)₂ O(CH₂)₂ --; R₄ ' is H, CH₃or CH₂ CH₃ ; R₅ is C₁ -C₅ alkyl optionally substituted with 1-3 atoms ofF, Cl or Br, or C₃ -C₄ alkenyl; R₆ is H, C₁ -C₄ alkyl or C₃ -C₄ alkenyl;R₇ is C₁ -C₄ alkyl; R₈ is H, CH₃ or OCH₃ ; A is ##STR281## W is O or S;X is H, Cl, Br, CH₃, CH₂ CH₃, C₁ -C₃ alkoxy, CF₃, SCH₃ or CH₂ OCH₃ ; Yis CH₃ or OCH₃ ; Z is CH, CCl, CBr, CCN, CCH₃, CCH₂ CH₃, CCH₂ CH₂ Cl orCCH₂ CH═CH₂ ; Y¹ is H, CH₃, OCH₃ or OCH₂ CH₃ ; and Q is O or CH₂ ; andtheir agriculturally suitable salts; provided that:(1) when R₁ is Cl,then L is Cl or Br and R₂ is H; (2) when R₃ is OCH₃, then R₄ is CH₃ ;(3) when W is S, then R₈ is H; and (4) when L is F, then R₁ is H, F, orC₁ -C₄ alkyl.
 2. A compound of claim 1 wherein Z is CH, CCl, CBr orCCH₃, W is O, and R₈ is H or CH₃.
 3. A compound of claim 2 wherein Z isCH and X is CH₃ or OCH₃.
 4. A compound of claim 3 wherein A is##STR282## L is Cl, Br or NR₃ R₄ and R₈ is H.
 5. A compound of claim 4wherein R₁ and R₂ are H.
 6. A compound of claim 5 wherein R is H.
 7. Acompound of claim 6 wherein L is Cl or Br.
 8. The compound of claim 1,2-(Dichloromethyl)-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide.9. The compound of claim 1,2-(Dichloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide.10. The compound of claim 1,2-(Chloromethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide.11. The compound of claim 1,2-(Chloromethyl)-N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide.12. The compound of claim 1,2-(1-Pyrrolidinylmethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide,hydrochloride.
 13. The compound of claim 1,2-(1-Pyrrolidinylmethyl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide.14. A compound selected from ##STR283## wherein R, R₁, R₂ and L are asdefined in claim 1; andZ is CH;provided that (1) when R₁ is Cl, then Lis Cl or Br and R₂ is H; (2) when L is NR₃ R₄ or N⁺ R₃ R₄ R₄ ', then R₃or R₄ can not be H; and (3) when R₃ is OCH₃, then R₄ is CH₃.